EP2341038A1 - Selective solar absorbent coating and manufacturing method - Google Patents
Selective solar absorbent coating and manufacturing method Download PDFInfo
- Publication number
- EP2341038A1 EP2341038A1 EP09821624A EP09821624A EP2341038A1 EP 2341038 A1 EP2341038 A1 EP 2341038A1 EP 09821624 A EP09821624 A EP 09821624A EP 09821624 A EP09821624 A EP 09821624A EP 2341038 A1 EP2341038 A1 EP 2341038A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layers
- metallic
- solar
- unique
- oxides
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 91
- 239000011248 coating agent Substances 0.000 title claims abstract description 83
- 230000002745 absorbent Effects 0.000 title claims abstract description 53
- 239000002250 absorbent Substances 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 63
- 239000002184 metal Substances 0.000 claims abstract description 51
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- 239000004411 aluminium Substances 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 239000003989 dielectric material Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- -1 silicon nitrides Chemical class 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 239000010931 gold Substances 0.000 claims description 12
- 239000010955 niobium Substances 0.000 claims description 12
- 150000004767 nitrides Chemical class 0.000 claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 238000005240 physical vapour deposition Methods 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 239000007769 metal material Substances 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical class [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 6
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- 229910001887 tin oxide Inorganic materials 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 235000014692 zinc oxide Nutrition 0.000 claims description 6
- 238000011282 treatment Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 4
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 3
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims 31
- 239000002344 surface layer Substances 0.000 claims 1
- 238000007669 thermal treatment Methods 0.000 claims 1
- 230000003667 anti-reflective effect Effects 0.000 abstract description 16
- 238000001228 spectrum Methods 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 239000007789 gas Substances 0.000 description 12
- 239000011651 chromium Substances 0.000 description 10
- 238000002835 absorbance Methods 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 230000003595 spectral effect Effects 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 230000008021 deposition Effects 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 3
- 238000005546 reactive sputtering Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical class [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical class [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical class [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000008713 feedback mechanism Effects 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003380 quartz crystal microbalance Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S70/00—Details of absorbing elements
- F24S70/20—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
- C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S70/00—Details of absorbing elements
- F24S70/20—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption
- F24S70/225—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption for spectrally selective absorption
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S70/00—Details of absorbing elements
- F24S70/20—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption
- F24S70/25—Coatings made of metallic material
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S70/00—Details of absorbing elements
- F24S70/30—Auxiliary coatings, e.g. anti-reflective coatings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B10/00—Integration of renewable energy sources in buildings
- Y02B10/20—Solar thermal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
Definitions
- the present invention refers to a selective absorbing coating that comprises of:. (i) a substrate, one or more metallic layers that confer low emissivity properties (ii) a structure of multiple alternating subnanometer thickness dielectric and metallic layers in which solar energy absorption is produced; and (iii) a layer or multilayered structure that provides antireflective properties.
- the invention also includes the method and process of manufacture and the use of said selective solar absorbent coating.
- the capture of solar energy in terms of the thermal capture aspect, is of increasing technological and economic importance from the point of view of hot water production, heating and refrigeration at a domestic level as well as electricity generation in solar thermoelectric power plants.
- absorbent coatings play an essential role.
- absorbent coatings such as those described in patents WO2005/121389 , US4582764 , US4628905 , US5523132 , US2004/0126594 , US2005/0189525 , US2007/0209658 , WO97/00335 , as well as several others.
- the absorbent coating consists of a metallic layer that provides low emissivity characteristics, one or more layers of dielectric materials doped with "Cermets" metallic elements, which act as absorbent layers for solar radiation and a dielectric layer that provides anti-reflective properties.
- the layers of cermets are absorbent layers, complex refraction index, where the capacity for absorption is provided by the co-dopant metal element whose concentration can be constant or gradual within each of the layers.
- Cermets are habitually oxides or metal nitrides doped with metallic elements such as Mo, Ni, Ti, Ta, Al, etc., that are usually deposited through codeposition techniques through reactive cathodic spraying "reactive sputtering".
- Codeposition through reactive sputtering consists in simultaneous evaporation of two materials through sputtering in the presence of, in addition to the inert gas, a reactive Gas, oxygen, nitrogen etc., residual in the deposition chamber. The residual gas reacts with one of the evaporated materials forming the corresponding dielectric compound, while part of the other compound is deposited in metal form.
- Reactive gas reacts both with the material that forms the dielectric compound and the doping metal, so to obtain the cermets with the appropriate absorption a stringent control of the stoichiometry process is required.
- the stoichiometry process is conditioned by the composition and partial pressures of the gases in the vacuum chamber in relation to the reactive gas consumption, and therefore depends on the evaporation speed, that is, cathode power, of its state, making accurate control of the stoichiometry process very difficult, requiring certain feedback mechanisms that can negatively affect the properties of the coatings.
- codopant metal also reacts with the reactive gas and forms dielectric compounds, so this metal does not therefore contribute to the absorption of the layer and requires large concentrations of codopant metal.
- this technique also presents limitations when choosing codopant metals as they should possess much less affinity for the reactive gas than the principal metal that forms the dielectric compound.
- Dielectric layers are deposited through reactive sputtering, including inert gas and reactive gas in the chamber or part of the chamber where dielectric coatings are deposited.
- Metal layers are deposited through DC sputtering, introducing inert gas exclusively in the chamber or part of the chamber where metallic layers are deposited.
- dielectric and metal layers are realised in different places and with different gas compositions, there is no limit to the composition of dielectric and metallic layers, which can even be taken from the same batch of metal, forming dielectric layers from a metal element, such as oxides or nitrides of a metal, and metal layers of the same element.
- a metal element such as oxides or nitrides of a metal
- the selective solar coating in this invention is designed to absorb solar energy and transform it into heat with low emissivity properties, facilitating and making the manufacturing process more robust and reliable and allowing greater possibilities for its design and optimisation.
- the coating deposited on the substrate which can be metallic or dielectric, ensures the mechanical and thermal stability of the coating, and is essentially characterised by including:
- Metal elements such as steel, stainless steel, copper or aluminium, and non-metallic elements such as glass, quartz or ceramic materials or polymers are included in this invention as substrate materials.
- the substrate can be subject to treatments, such as the oxidation of the superficial layer or thermal and cleaning treatments that optimise adhesion of the coating and therefore its mechanical and environmental stability.
- the current invention includes a coating absorbent of solar energy and reflective in medium-far infrared, that contains one or more metal layers on the substrate, highly reflective in medium-far infrared, a multilayered structure with thin alternating metallic-dielectric layers and one or more dielectric layers that form the antireflective structure for solar energy.
- the coating is unique because of the highly reflective metal layer or layers deposited on the substrate include a metallic material selected from the group formed by silver (Ag), gold (Au), aluminium (Al), chromium (Cr), molybdenum. (Mo), copper (Cu), nickel (Ni), titanium (Ti), niobium (Nb), tantalum (Ta), tungsten (W), palladium (Pd) or an alloy of the same or mixtures of the same.
- the layers of dielectric material in the absorbent multi-layer structure consist in metal oxides and/or metal nitride elements, with a refraction index of between 1.4 and 2.4.
- the coating is distinguished because the metal oxides are selected from the group consisting of tin oxides, zinc oxides, aluminium oxides, titanium oxides, silicon dioxides, nickel oxides, chromium oxides, indium oxides or a mixture of the same.
- the coating, according to the invention is unique because the nitrides of metal elements are selected from the group formed by silicon nitrides, chromium nitrides and aluminium nitrides, or mixtures of the same.
- the coating is unique because the metal layers that form part of the absorbent multilayered structure are made from a metal selected from the group formed by silver (Ag), gold (Au), aluminium (Al), chromium (Cr), molybdenum (Mo), copper (Cu) nickel (Ni), titanium (Ti), niobium (Nb), tantalum (Ta), tungsten (W), palladium (Pd) or any alloy of the same or mixture of the same.
- a metal selected from the group formed by silver (Ag), gold (Au), aluminium (Al), chromium (Cr), molybdenum (Mo), copper (Cu) nickel (Ni), titanium (Ti), niobium (Nb), tantalum (Ta), tungsten (W), palladium (Pd) or any alloy of the same or mixture of the same.
- the invention equally contemplates the presence of one or more dielectric layers that act as an antireflective structure and these are made from metal oxides and/or metal nitride elements, with a refraction index between 1.4 and 2.4.
- the coating, according to the invention is unique because metal oxides are selected from the group formed by tin oxides, zinc oxides, aluminium oxides, titanium oxides, silicon dioxides, nickel oxides, chromium oxides, indium oxides or mixtures of the same.
- the coating, according to the invention is unique because the nitrides of metal elements are selected the group formed by silicon nitrides, chromium nitrates and aluminium nitrides, or mixtures of the same.
- metal alloy means any of those that these metals can form between them or with other metals.
- the thickness of each of the reflecting metallic layers in medium-far infrared, and each of the layers of dielectric material of the antireflective structure is between 1 and 500 nm.
- the thickness of each of the metallic and dielectric layers of the absorbing multilayered structured is less than 10nm, with a total number of layers of the multilayered structure of more than 20.
- the multilayered structure can be configured as a homogenous zone, in which all the dielectric layers are of the same material and have the same thickness and all the metal layers are of the same metal and thickness, in various differentiated zones, in which each zones is configured as a homogenous zone and differs from the other zones in the material used for the dielectric layers and/or the metal used for the metal layers and/or the thickness of each of the metallic or dielectric layers, or can be configured as a gradual zone where the thickness of the metal and/or dielectric layers vary gradually.
- the preference is for the multilayered structure to be configured with at least two differentiated zones, in which the composition and/or thickness of the layers of one of the areas is different to the composition and/or thickness of the other.
- the total number of layers of coating is over 25 and the total thickness is between 100 nm and 2000 nm.
- the purpose of the invention is the fact that the different layers of coating are deposited through physical deposition techniques in vacuum in vapour phase (PVD, physical vapour deposition) such as thermal evaporation, electron gun, ionic implantation or "sputtering", by chemical deposition in vapour phase (CVD, chemical vapour deposition) or through electrolytic baths, with the sputtering technique being the preferred method for this task.
- PVD vacuum in vapour phase
- CVD chemical vapour phase
- electrolytic baths electrolytic baths
- Another purpose of this invention is the use of the coating in absorbent tubes for parabolic cylinder collectors in solar thermoelectric plants.
- Another purpose of this invention is the use of the coating in solar panels for hot water; heating or household refrigeration, both in the form of absorbent tubes as well as absorbent plates.
- This invention also has the benefit that the coating can be used in capture systems at solar tower-type thermoelectric power plants, in which solar energy reflected by a multitude of heliostats is concentrated in the capture system positioned in a tower.
- the selective solar radiation absorbing coating in the invention includes, as shown in figs. 1 to 4 , at least one substrate (1), at least one reflective metallic layer (2) that provides low emissivity properties, a multilayered structure (3) of alternating dielectric (5) and metallic (6) layers that act as an absorbent structure for the solar radiation and al least one dielectric layer (4) that acts as an antireflective structure.
- the substrate (1) can be a metallic or dielectric material or a combination of both, that ensures mechanical stability of the coating.
- the metallic reflecting layer (2) consists, in turn, of at least one highly reflective layer in medium-far infrared (2.5-20 ⁇ m wave length), said metallic layer being deposited on the substrate itself.
- the absorbent multilayered structure (3) consists, in turn, in a series of alternating dielectric (5) and metallic (6) layers, deposited on the reflecting metallic layer (2), and can be of the same or different thickness and/or composition:
- the antireflective structure (4) consists in at least one dielectric layer that provides solar energy antireflective properties.
- Figures 1-4 show specific examples of selective absorbent coatings, according to the invention, in which a reflective layer (2) has been placed on the substrate (1), and on that has been placed a multilayered absorbent structure (3) consisting in a single zone, in two zones, in n zones and in a single zone with thicknesses of the dielectric and metallic layers that vary in said zone, and an antireflective layer (4) placed on the multilayered structure.
- the substrates (1) correspond to metals such as steel, stainless steel, copper and aluminium and dielectrics such as glass, quartz, polymeric materials or ceramic materials, or a combination of different materials.
- the reflective metal layer (2) silver (Ag), gold (Au), aluminium (Al), chromium (Cr), Molybdenum (Mo), Copper (Cu), nickel (Ni), titanium (Ti), niobium (Nb), tantalum (Ta), tungsten (W), palladium (Pd) or a mixture of two or more of these or an alloy of said metals are used.
- These metal layers (2) have a thickness of between 5 and 1000 nm.
- the layers of dielectric material (5) of the different configurations of absorbent multilayered structures have a refraction index of between 1.4 and 2.4.
- metal oxides and/or metal element nitrides such as tin oxides zinc oxides, aluminium oxides, titanium oxides, silicon dioxides, silicon-aluminium, nickel oxides, chromium oxides, niobium oxides, tantalum oxides or mixtures of the same are used; as well as silicon nitrides, chromium nitrides and aluminium nitrides , or mixtures of the same.
- the thickness of the dielectric layers (5) is less than 10 nm, preferably below 1nm, the number of dielectric layers is more that 10, and the total thickness of the dielectric layers of the absorbent layer structure (3) is between 5 and 1000 nm.
- the metal layers (6) of the different configurations of the absorbent multilayer structures silver (Ag), gold (Au) aluminium (Ai), chromium (Cr), Molybdenum (Mo), copper (Cu), nickel (Ni), titanium (Ti), niobium (Nb), tantalum (Ta), Tungsten (W) palladium (Pd), or an alloy of the same or mixtures of the same are used.
- the thickness of the metal layers (6) are less than 10nm, preferably below 1nm, the number of metal layers is above 10, and the total thickness of the metal layers of the absorbent multilayered structure (3) is between 5 and 1000 nm.
- the layers that form the antireflective structure (4) have a refraction index of between 1.4 and 2.4.
- metal oxides and/or nitrides of metal elements are used, such as tin oxide, zinc oxide, aluminium oxide, titanium oxides, silicon oxides, silicon-aluminium oxides, nickel oxides, or mixtures of the same; as well as silicon nitrides and aluminium nitrides, or mixtures of the same.
- the thickness of the layers of dielectric material of the antireflective structure is between 5 and 1000 nm..
- the substrate can be subjected to diverse treatments, such as the oxidation of the superficial layer or thermal and cleaning treatments, since improving the adhesion of the coating implies more mechanical and environmental stability.
- a first metal layer is placed (2) onto the substrate (1) of the metal or dielectric material, and onto this is placed the first metal layer (2), and onto this is deposited the first of the layers that form the absorbent multilayered structure, with the first layer being either the dielectric (5) or metal (6) material.
- the rest of the metal (6) and dielectric (5) layers are alternately deposited, and can have identical or different thicknesses and/or compositions, forming the absorbent multilayered structure.
- the different layers that form the antireflective structure are added.
- a metal and/or dielectric compound deposition procedure is used, such as chemical vapour deposition (CVD) or physical vapour deposition (PVD).
- CVD chemical vapour deposition
- PVD physical vapour deposition
- the selective solar absorbent coating of the invention can be used as a coating for laminar materials or tubes selected from the group formed by steel, stainless steel, copper, aluminium or ceramic materials, in the absorbent elements of tower-type solar thermoelectric power plants and for use in absorbent element in stirling dish systems or for use in absorbent tubes of solar thermoelectric power plants with parabolic-cylinder collectors.
- coatings according to the invention are shown below, as well as their reflectance properties and absorbance at different wave lengths. Said examples allow for the visualisation of the coating's properties.
- EXAMPLE 1 Selective absorbing coating with absorbent structure of two zones,based on molybdenum (Mo) and aluminium silicon oxide (SiAIO x ).
- a layer of Mo of 300nm is deposited on a substrate (1) of stainless steel 304 .
- the absorbent multilayer structure consisting in two differentiated zones is deposited.
- the first zone has a total thickness of 52 nm, and consists in 285 layers of SiAIO x with a thickness of 0.08 nm alternated with another 285 of Mo with a thickness of 0.1 nm.
- the second zone has a total thickness of 57nm, and consists in 390 layers of SiAIO x with a thickness of 0.08 nm alternated with another 390 of Mo with a thickness of 0.06 nm.
- the thickness of each of these layers is understood to mean the average thickness obtained from the data provided by a quartz crystal microbalance.
- an antireflective reflective layer of SiAIO x with a thickness or 87nm has been deposited on the absorbent multilayer structure.
- a spectroscopic study of the coating in example 1 was performed and Fig. 5 shows the reflectance in the spectral visible-infrared range, together with the solar energy spectrum and the thermal emission spectrum at 400°C.
- the coating show low reflectance values in the solar spectrum zone, which means high absorbance, and high reflectance in the thermal emission zone, which means low emissivity. Determining global values, a solar absorbance of around 97.5% is obtained and an emissivity at 400°C of around 0,15, which shows the suitability of the coating for use in thermal solar collectors and CCP solar collectors for thermoelectric plants.
- EXAMPLE 2 Selective absorbing coating with absorbent structure of two nickel (Ni) based zones a silicon-aluminium oxide (SiAIO x ).
- a layer of Ni of 110 nm is deposited on a substrate (1) or stainless steel 304 .
- the absorbent multilayer structure consisting in two differentiated zones is deposited.
- the first zone has a total thickness of 78 nm and consists in 340 layers of SiAIO x with a thickness of 0.085 nm alternated with another 340 of Ni with a thickness of 0.145 nm.
- the second zone has a total thickness of 55 nm, and consists in 490 layers of SiAIO x with a thickness of 0.08 nm alternated with another 490 of Ni with a thickness of 0.03 nm.
- the thickness of each of these layers is understood to mean the average thickness obtained from the data provided by a crystal quartz microbalance.
- On the absorbent multi-layer structure is placed an antireflective layer of SiAIOx with a thickness of 67nm.
- a spectroscope study of the coating of example 2 was performed and Fig. 6 shows the reflectance in the spectral visible-infrared range, together with the solar energy spectrum and the thermal emission spectrum at 400°C.
- the coating shows low reflectance values in the solar spectrum zone, which means high absorbance, and high reflectance in the thermal emission zone, which means low emissivity. Determining global values, a solar absorbance of around 97.5% and emissivity at 400°C around 0.08 was obtained, which demonstrates the suitability of the coating for its use in CCP solar thermal collectors for thermoelectric plants.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Thermal Sciences (AREA)
- Combustion & Propulsion (AREA)
- General Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Ceramic Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Laminated Bodies (AREA)
- Surface Treatment Of Glass (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
- The present invention refers to a selective absorbing coating that comprises of:. (i) a substrate, one or more metallic layers that confer low emissivity properties (ii) a structure of multiple alternating subnanometer thickness dielectric and metallic layers in which solar energy absorption is produced; and (iii) a layer or multilayered structure that provides antireflective properties.
- The invention also includes the method and process of manufacture and the use of said selective solar absorbent coating.
- The capture of solar energy, in terms of the thermal capture aspect, is of increasing technological and economic importance from the point of view of hot water production, heating and refrigeration at a domestic level as well as electricity generation in solar thermoelectric power plants.
- These systems require maximum solar energy absorption and the minimum possible loss of energy. With this end in mind, these systems are configured in vacuum tubes or similar structures that reduce losses by conduction and convection and possess coatings with a great capacity for solar energy absorption and low emissivity characteristics to reduce energy losses through thermal radiation in far infrared.
- Consequently, in the domestic area as well as in the production of electricity, selective absorbent coatings play an essential role. There are numerous records of absorbent coatings such as those described in patents
WO2005/121389 ,US4582764 ,US4628905 ,US5523132 ,US2004/0126594 ,US2005/0189525 ,US2007/0209658 ,WO97/00335 - Cermets are habitually oxides or metal nitrides doped with metallic elements such as Mo, Ni, Ti, Ta, Al, etc., that are usually deposited through codeposition techniques through reactive cathodic spraying "reactive sputtering". Codeposition through reactive sputtering consists in simultaneous evaporation of two materials through sputtering in the presence of, in addition to the inert gas, a reactive Gas, oxygen, nitrogen etc., residual in the deposition chamber. The residual gas reacts with one of the evaporated materials forming the corresponding dielectric compound, while part of the other compound is deposited in metal form. Reactive gas reacts both with the material that forms the dielectric compound and the doping metal, so to obtain the cermets with the appropriate absorption a stringent control of the stoichiometry process is required. The stoichiometry process is conditioned by the composition and partial pressures of the gases in the vacuum chamber in relation to the reactive gas consumption, and therefore depends on the evaporation speed, that is, cathode power, of its state, making accurate control of the stoichiometry process very difficult, requiring certain feedback mechanisms that can negatively affect the properties of the coatings.
- Likewise, part of the codopant metal also reacts with the reactive gas and forms dielectric compounds, so this metal does not therefore contribute to the absorption of the layer and requires large concentrations of codopant metal. Besides, this technique also presents limitations when choosing codopant metals as they should possess much less affinity for the reactive gas than the principal metal that forms the dielectric compound.
- This invention seeks to resolve all the difficulties set out above, as each of the cermets layers are replaced by an alternating multilayered dielectric and metal structure, with very think layers, less than 10nm and mainly under 1nm. Dielectric layers are deposited through reactive sputtering, including inert gas and reactive gas in the chamber or part of the chamber where dielectric coatings are deposited. Metal layers are deposited through DC sputtering, introducing inert gas exclusively in the chamber or part of the chamber where metallic layers are deposited. As a result, precise control of the stoichiometry process is not required, since the depositing of the dielectric layers requires a composition of gases that guarantees the total reaction of the evaporated metal, while the metal nature of the alternating layers is determined by the inert gas introduced as process gas. As the depositing of both types of materials is realised in different chambers or in isolated parts of the same deposition chamber, gas mixture is minimal and no chemical reaction of the constituent material of the metal layers is produced. Likewise, as the deposition of dielectric and metal layers is realised in different places and with different gas compositions, there is no limit to the composition of dielectric and metallic layers, which can even be taken from the same batch of metal, forming dielectric layers from a metal element, such as oxides or nitrides of a metal, and metal layers of the same element.
- The selective solar coating in this invention is designed to absorb solar energy and transform it into heat with low emissivity properties, facilitating and making the manufacturing process more robust and reliable and allowing greater possibilities for its design and optimisation. The coating deposited on the substrate, which can be metallic or dielectric, ensures the mechanical and thermal stability of the coating, and is essentially characterised by including:
- At least one highly reflective metallic layer in far infrared (spectral range between 5 and .
50 µm wave length) that provides low emissivity characteristics of the coating deposited on the substrate. - A multilayered structure deposited on the reflective layer, that provides solar radiation absorbing properties, formed by alternating metallic and dielectric layers of a very small thickness (less than 10nm and generally less than 1nm), that can be homogenous for metallic layers, on the one hand, and dielectric, on the other, throughout the structure, differentiated in various zones or with thicknesses that gradually vary along the structure.
- At least one dielectric layer deposited on the absorbing multilayered structure that acts as an antireflective layer.
- Metal elements such as steel, stainless steel, copper or aluminium, and non-metallic elements such as glass, quartz or ceramic materials or polymers are included in this invention as substrate materials. The substrate can be subject to treatments, such as the oxidation of the superficial layer or thermal and cleaning treatments that optimise adhesion of the coating and therefore its mechanical and environmental stability.
- Likewise, the current invention includes a coating absorbent of solar energy and reflective in medium-far infrared, that contains one or more metal layers on the substrate, highly reflective in medium-far infrared, a multilayered structure with thin alternating metallic-dielectric layers and one or more dielectric layers that form the antireflective structure for solar energy. The coating, according to the invention, is unique because of the highly reflective metal layer or layers deposited on the substrate include a metallic material selected from the group formed by silver (Ag), gold (Au), aluminium (Al), chromium (Cr), molybdenum. (Mo), copper (Cu), nickel (Ni), titanium (Ti), niobium (Nb), tantalum (Ta), tungsten (W), palladium (Pd) or an alloy of the same or mixtures of the same.
- According to another characteristic of the invention, the layers of dielectric material in the absorbent multi-layer structure consist in metal oxides and/or metal nitride elements, with a refraction index of between 1.4 and 2.4. The coating, according to the invention, is distinguished because the metal oxides are selected from the group consisting of tin oxides, zinc oxides, aluminium oxides, titanium oxides, silicon dioxides, nickel oxides, chromium oxides, indium oxides or a mixture of the same. Correspondingly, the coating, according to the invention, is unique because the nitrides of metal elements are selected from the group formed by silicon nitrides, chromium nitrides and aluminium nitrides, or mixtures of the same.
- Likewise, the coating, according to the invention, is unique because the metal layers that form part of the absorbent multilayered structure are made from a metal selected from the group formed by silver (Ag), gold (Au), aluminium (Al), chromium (Cr), molybdenum (Mo), copper (Cu) nickel (Ni), titanium (Ti), niobium (Nb), tantalum (Ta), tungsten (W), palladium (Pd) or any alloy of the same or mixture of the same.
- The invention equally contemplates the presence of one or more dielectric layers that act as an antireflective structure and these are made from metal oxides and/or metal
nitride elements, with a refraction index between 1.4 and 2.4. The coating, according to the invention, is unique because metal oxides are selected from the group formed by tin oxides, zinc oxides, aluminium oxides, titanium oxides, silicon dioxides, nickel oxides, chromium oxides, indium oxides or mixtures of the same. Correspondingly, the coating, according to the invention, is unique because the nitrides of metal elements are selected the group formed by silicon nitrides, chromium nitrates and aluminium nitrides, or mixtures of the same. - In the context of the current invention the term "metallic alloy" means any of those that these metals can form between them or with other metals.
- According to another characteristic of the invention, the thickness of each of the reflecting metallic layers in medium-far infrared, and each of the layers of dielectric material of the antireflective structure is between 1 and 500 nm. In addition, according to another characteristic of the invention, the thickness of each of the metallic and dielectric layers of the absorbing multilayered structured is less than 10nm, with a total number of layers of the multilayered structure of more than 20. The multilayered structure can be configured as a homogenous zone, in which all the dielectric layers are of the same material and have the same thickness and all the metal layers are of the same metal and thickness, in various differentiated zones, in which each zones is configured as a homogenous zone and differs from the other zones in the material used for the dielectric layers and/or the metal used for the metal layers and/or the thickness of each of the metallic or dielectric layers, or can be configured as a gradual zone where the thickness of the metal and/or dielectric layers vary gradually. The preference is for the multilayered structure to be configured with at least two differentiated zones, in which the composition and/or thickness of the layers of one of the areas is different to the composition and/or thickness of the other.
- All in all, the total number of layers of coating is over 25 and the total thickness is between 100 nm and 2000 nm.
- The purpose of the invention is the fact that the different layers of coating are deposited through physical deposition techniques in vacuum in vapour phase (PVD, physical vapour deposition) such as thermal evaporation, electron gun, ionic implantation or "sputtering", by chemical deposition in vapour phase (CVD, chemical vapour deposition) or through electrolytic baths, with the sputtering technique being the preferred method for this task.
- Another purpose of this invention is the use of the coating in absorbent tubes for parabolic cylinder collectors in solar thermoelectric plants.
- Another purpose of this invention is the use of the coating in solar panels for hot water; heating or household refrigeration, both in the form of absorbent tubes as well as absorbent plates.
- This invention also has the benefit that the coating can be used in capture systems at solar tower-type thermoelectric power plants, in which solar energy reflected by a multitude of heliostats is concentrated in the capture system positioned in a tower.
- And, finally, it is also the purpose of this invention to use the coating in the capture system of stirling dish systems.
- With the aim of illustrating the advantages and properties of the coating in this invention and with the object of better understanding the characteristics of the invention, a detailed description of the ideal scenario will be provided, based on a set of drawings enclosed with this specification, where the following, for illustration but not limiting purposes, are represented:
-
Fig. 1 shows a drawing of the transverse section of a coating, according to the invention, with the dielectric and metallic layers of the absorbent multilayered structure of the same material and thickness across the entire structure. -
Fig. 2 shows a drawing of the transverse section of the coating, in accordance with the invention, in which the absorbent multilayered structure is divided in two zones where the dielectric and metallic layers are of a different composition and thickness in each zone. -
Fig. 3 shows a drawing of the transverse section of the coating, in accordance with the invention, where the absorbent multilayered structure is divided into several zones and the dielectric and metallic layers are of a different composition and thickness in each zone. -
Fig. 4 shows a drawing of the transverse section of a coating, according to the invention, in which the absorbent multilayered structure includes only one area in which the dielectric and metallic layers vary in thickness progressively within the zone. -
Fig. 5 shows the reflectance in the spectral visible-infrared range of the structure in example 1, together with the solar energy spectrum and thermal emission spectrum at 400°C. -
Fig. 6 shows the reflectance in the spectral visible-infrared range of the structure in example 2, together with the solar energy spectrum and thermal emission spectrum at 400°C temperature. - In the above figures the numerical references correspond to the following parts and elements.
- 1.- Substrate
- 2.- Reflective metallic layer
- 3.- Absorbent multilayered structure
- 4.- Antireflecting dielectric structure
- 5.- Dielectric layer
- 6.- Metallic layer
- 7.-
Multilayered structure zone 1 - 8.-
Multilayered structure zone 2 - 9.- Multilayered structure zone n
- The selective solar radiation absorbing coating in the invention includes, as shown in
figs. 1 to 4 , at least one substrate (1), at least one reflective metallic layer (2) that provides low emissivity properties, a multilayered structure (3) of alternating dielectric (5) and metallic (6) layers that act as an absorbent structure for the solar radiation and al least one dielectric layer (4) that acts as an antireflective structure. - The substrate (1) can be a metallic or dielectric material or a combination of both, that ensures mechanical stability of the coating.
- The metallic reflecting layer (2) consists, in turn, of at least one highly reflective layer in medium-far infrared (2.5-20µm wave length), said metallic layer being deposited on the substrate itself.
- The absorbent multilayered structure (3) consists, in turn, in a series of alternating dielectric (5) and metallic (6) layers, deposited on the reflecting metallic layer (2), and can be of the same or different thickness and/or composition:
- a) Dielectric layers (5) can be identical to each other, that is to say, of the same material and thickness, and the same is true for the metallic layers (6) which
configure the multilayered structure in a unique differentiated zone represented infig. 1 . - b) In a similar manner, there can be two types of dielectric layers (5) with different material and/or thickness and the same is true for the metallic layers (6) configuring the absorbent structure in two differentiated zones, with the first zone (7) consisting in dielectric and metallic layers of one type and the second zone (8) of another type, as seen in
figure 2 . - c) There can be several types of dielectric layers (5) and several types of metallic layers (6), configuring the structure in n zones, with n being an unlimited number of zones where the absorbent multilayer structure consists in a first zone (7), a second zone (8) and so on until the final n zone (9) with each formed by a type of dielectric layer and a type of metallic layer as seen in
figure 3 . - d) In the same way, the absorbent structure can consist in dielectric layers (5) and metallic layers (6) whose thickness gradually varies along the structure, configuring a single zone but with variable thicknesses in the different layers, metallic and/or dielectric, as shown in
fig. 4 . - The antireflective structure (4) consists in at least one dielectric layer that provides solar energy antireflective properties.
-
Figures 1-4 show specific examples of selective absorbent coatings, according to the invention, in which a reflective layer (2) has been placed on the substrate (1), and on that has been placed a multilayered absorbent structure (3) consisting in a single zone, in two zones, in n zones and in a single zone with thicknesses of the dielectric and metallic layers that vary in said zone, and an antireflective layer (4) placed on the multilayered structure. - The substrates (1) correspond to metals such as steel, stainless steel, copper and aluminium and dielectrics such as glass, quartz, polymeric materials or ceramic materials, or a combination of different materials.
- For the reflective metal layer (2) silver (Ag), gold (Au), aluminium (Al), chromium (Cr), Molybdenum (Mo), Copper (Cu), nickel (Ni), titanium (Ti), niobium (Nb), tantalum (Ta), tungsten (W), palladium (Pd) or a mixture of two or more of these or an alloy of said metals are used. These metal layers (2) have a thickness of between 5 and 1000 nm.
- The layers of dielectric material (5) of the different configurations of absorbent multilayered structures have a refraction index of between 1.4 and 2.4. For this purpose metal oxides and/or metal element nitrides, such as tin oxides zinc oxides, aluminium oxides, titanium oxides, silicon dioxides, silicon-aluminium, nickel oxides, chromium oxides, niobium oxides, tantalum oxides or mixtures of the same are used; as well as silicon nitrides, chromium nitrides and aluminium nitrides , or mixtures of the same. The thickness of the dielectric layers (5) is less than 10 nm, preferably below 1nm, the number of dielectric layers is more that 10, and the total thickness of the dielectric layers of the absorbent layer structure (3) is between 5 and 1000 nm.
- For the realisation of the metal layers (6) of the different configurations of the absorbent multilayer structures silver (Ag), gold (Au) aluminium (Ai), chromium (Cr), Molybdenum (Mo), copper (Cu), nickel (Ni), titanium (Ti), niobium (Nb), tantalum (Ta), Tungsten (W) palladium (Pd), or an alloy of the same or mixtures of the same are used. The thickness of the metal layers (6) are less than 10nm, preferably below 1nm, the number of metal layers is above 10, and the total thickness of the metal layers of the absorbent multilayered structure (3) is between 5 and 1000 nm.
- The layers that form the antireflective structure (4) have a refraction index of between 1.4 and 2.4. For this purpose, metal oxides and/or nitrides of metal elements are used, such as tin oxide, zinc oxide, aluminium oxide, titanium oxides, silicon oxides, silicon-aluminium oxides, nickel oxides, or mixtures of the same; as well as silicon nitrides and aluminium nitrides, or mixtures of the same. The thickness of the layers of dielectric material of the antireflective structure is between 5 and 1000 nm..
- Finally, with the idea of increasing adherence between the coating and the substrate, the substrate can be subjected to diverse treatments, such as the oxidation of the superficial layer or thermal and cleaning treatments, since improving the adhesion of the coating implies more mechanical and environmental stability.
- So to obtain the coating of the invention in a manner that a first metal layer is placed (2) onto the substrate (1) of the metal or dielectric material, and onto this is placed the first metal layer (2), and onto this is deposited the first of the layers that form the absorbent multilayered structure, with the first layer being either the dielectric (5) or metal (6) material. After this first layer the rest of the metal (6) and dielectric (5) layers are alternately deposited, and can have identical or different thicknesses and/or compositions, forming the absorbent multilayered structure. After the last of the layers of the absorbent multilayered structure, the different layers that form the antireflective structure are added.
- For the successive addition of the different layers (2, 4, 5, 6...) to the transparent (1) substrate, a metal and/or dielectric compound deposition procedure is used, such as
chemical vapour deposition (CVD) or physical vapour deposition (PVD). The preferred manner, within the range of PVD techniques, is "magnetron sputtering". - To determine solar absorbance and thermal emissivity, an spectroscopic study of the coating is carried out, studying the reflectance in the spectral visible-infrared range, together with the solar energy spectrum and thermal emission spectrum at 400°C, giving low reflectance values in the solar spectrum zone, which means high absorbance (above or equal to 95%), and high reflectance values in the thermal emission zone, which mean low emissivity (less than or equal to 0.2).
- Evidently, variants of the described procedure exist, known by experts in the field, which depend on which materials are used and the use of the coatings obtained.
- The selective solar absorbent coating of the invention can be used as a coating for laminar materials or tubes selected from the group formed by steel, stainless steel, copper, aluminium or ceramic materials, in the absorbent elements of tower-type solar thermoelectric power plants and for use in absorbent element in stirling dish systems or for use in absorbent tubes of solar thermoelectric power plants with parabolic-cylinder collectors.
- Some examples of coatings according to the invention are shown below, as well as their reflectance properties and absorbance at different wave lengths. Said examples allow for the visualisation of the coating's properties.
- On a substrate (1) of stainless steel 304 a layer of Mo of 300nm is deposited. On this layer of Mo the absorbent multilayer structure consisting in two differentiated zones is deposited. The first zone has a total thickness of 52 nm, and consists in 285 layers of SiAIOx with a thickness of 0.08 nm alternated with another 285 of Mo with a thickness of 0.1 nm. The second zone has a total thickness of 57nm, and consists in 390 layers of SiAIOx with a thickness of 0.08 nm alternated with another 390 of Mo with a thickness of 0.06 nm. The thickness of each of these layers is understood to mean the average thickness obtained from the data provided by a quartz crystal microbalance. On the absorbent multilayer structure an antireflective reflective layer of SiAIOx with a thickness or 87nm has been deposited.
- With the aim of determining solar absorbance and thermal emissivity, a spectroscopic study of the coating in example 1 was performed and
Fig. 5 shows the reflectance in the spectral visible-infrared range, together with the solar energy spectrum and the thermal emission spectrum at 400°C. The coating show low reflectance values in the solar spectrum zone, which means high absorbance, and high reflectance in the thermal emission zone, which means low emissivity. Determining global values, a solar absorbance of around 97.5% is obtained and an emissivity at 400°C of around 0,15, which shows the suitability of the coating for use in thermal solar collectors and CCP solar collectors for thermoelectric plants. - On a substrate (1) or stainless steel 304 a layer of Ni of 110 nm is deposited. On this layer of Ni the absorbent multilayer structure consisting in two differentiated zones is deposited. The first zone has a total thickness of 78 nm and consists in 340 layers of SiAIOx with a thickness of 0.085 nm alternated with another 340 of Ni with a thickness of 0.145 nm. The second zone has a total thickness of 55 nm, and consists in 490 layers of SiAIOx with a thickness of 0.08 nm alternated with another 490 of Ni with a thickness of 0.03 nm. The thickness of each of these layers is understood to mean the average thickness obtained from the data provided by a crystal quartz microbalance. On the absorbent multi-layer structure is placed an antireflective layer of SiAIOx with a thickness of 67nm.
- With the aim of determining solar absorbance and thermal emissivity, a spectroscope study of the coating of example 2 was performed and
Fig. 6 shows the reflectance in the spectral visible-infrared range, together with the solar energy spectrum and the thermal emission spectrum at 400°C. The coating shows low reflectance values in the solar spectrum zone, which means high absorbance, and high reflectance in the thermal emission zone, which means low emissivity. Determining global values, a solar absorbance of around 97.5% and emissivity at 400°C around 0.08 was obtained, which demonstrates the suitability of the coating for its use in CCP solar thermal collectors for thermoelectric plants.
Claims (29)
- Solar selective absorbing coating with solar absorbing properties and low emissivity, unique because it consists in:- a substrate (1) of metallic, dielectric or ceramic material,- at least one metallic layer (2) that is highly reflecting in medium-far infrared, deposited on the substrate (1),- an absorbing multilayer structure (3) deposited on the reflecting metallic layer (2), composed of alternating dielectric (5) layers of equal or different thickness and/or composition, and- at least one anti-reflecting dielectric layer (4), deposited on the absorbing multilayer structure (3).
- Solar absorbing coating with solar absorbent properties and low emissivity, according to claim 1, unique because the absorbing multilayer structure (3) consists in a homogeneous area with the dielectric layers (5) with equal composition and the metallic layers (6) with equal composition.
- Solar selective absorbing coating according to claim 1 unique because the absorbing multilayer structure (3) consists in two or more homogeneous areas so that the dielectric layers (5) differ in material or composition from one area to another, and the metallic layers (6) differ in material or composition from one area to another.
- Solar selective absorbing coating with solar absorbent properties and low emissivity, according to claims 2 and 3 unique because, within a homogeneous area the metallic layers (6) among themselves and/or the dielectric layers (5) among themselves, have different thicknesses.
- Solar selective absorbing coating with solar absorbent properties and low emissivity, according to claim 4 unique because the thickness varies gradually throughout the area.
- Solar selective absorbing coating with solar absorbent properties and low emissivity, according to claims 2 and 3 unique because, within a homogeneous area, the metallic layers (6) among themselves and/or dielectric layers (5) among themselves, have equal thicknesses.
- Solar selective absorbing coating according to any of the above claims, unique because the substrate (1) is a metallic material of the group formed by steel, stainless steel, copper or aluminium or their combination.
- Solar selective absorbing coating according to claim 7, unique because the substrate (1) of metallic material has been subjected to treatment for oxidation of the surface layer or to thermal treatments.
- Solar selective absorbing coating according to claims 1-6, unique because the substrate (1) is a dielectric material of the group formed by glass, quartz, polymeric materials or ceramic materials, or their combination.
- Solar selective absorbing coating according to any of the above claims, unique because the highly reflecting metallic layers (2) consist in a metallic material selected from the silver (Ag), gold (Au), aluminium (Al), chrome (Cr), molybdenum (Mo), copper (Cu), nickel (Ni), titanium (Ti), niobium (Nb), tantalum (Ta), tungsten (W), palladium (Pd) group or a mixture of two or more of them or an alloy of these metals.
- Solar selective absorbing coating according to any of the above claims, unique because the layers of dielectric material (5) of the absorbing structure (3) consist in metallic oxides and/or nitrides of metallic elements, with a refraction index of between 1.4 and 2.4.
- Solar selective absorbing coating according to claim 11, unique because the dielectric materials (5) are metallic oxides selected from the group formed by tin oxides, zinc oxides, aluminium oxides, titanium oxides, silicon oxides, nickel oxides, chrome oxides, niobium oxides, tantalum oxides or mixtures of them and/or nitrides of metallic elements selected from the group formed by silicon nitrides, chrome nitrides and aluminium nitrides, or mixtures of them.
- Solar selective absorbing coating according to any of the above claims, unique because the metallic layers (6) of the absorbing structure (3) consist in a metallic material selected from the group formed by silver (Ag), gold (Au), aluminium (Al), chrome (Cr), molybdenum (Mo), copper (Cu), nickel (Ni), titanium (Ti), niobium (Nb), tantalum (Ta), tungsten (W), palladium (Pd) or a mixture of two or more of them or an alloy of these metals.
- Solar selective absorbing coating according to any of the above claims, unique because the anti-reflecting dielectric layers (4) consist in metallic oxides and/or nitrides of metallic elements, with a refraction index of between 1.4 and 2.4.
- Solar selective absorbing coating according to claim 14, unique because the anti-reflecting dielectric layers (4) are metallic oxides selected from the group formed by tin oxides, zinc oxides, aluminium oxides, titanium oxides, silicon oxides, nickel oxides, chrome oxides, niobium oxides, tantalum oxides or mixtures of them or nitrides of metallic elements selected from the group formed by silicon nitrides, chrome nitrides and aluminium nitrides, or mixtures of them.
- Solar selective absorbing coating according to any of the above claims, unique because the thickness of each of the highly reflecting metallic layers (2) is between 5 and 1000 nm.
- Solar selective absorbing coating according to any of the above claims, unique because the thickness of each of the anti-reflecting dielectric material layers (4) is between 5 and 1000 nm.
- Solar selective absorbing coating according to any of the above claims, unique because the thickness of each of the metallic (6) and dielectric (5) layers of the absorbing multilayer structure (3) is less than 10 nm and preferably less than 1 nm, and the overall thickness of the absorbing multilayer structure (3) is between 5 and 1000 nm.
- Solar selective absorbing coating according to claim 18, unique because the thickness of each of the metallic (6) and dielectric (5) layers of the absorbing multilayer structure (3) is less than 1 nm.
- Solar selective absorbing coating according to any of the above claims, unique because the different layers that compose the absorbent coating are deposited by means of physical vapour deposition (PVD).
- Solar selective absorbing coating according to claim 20, unique because the different layers that compose the absorbent coating are deposited by means of the "magnetron sputtering" technique.
- Solar selective absorbing coating according to any of the above claims, unique because it has solar absorbency over 95% and emissivity at 400°C less than 0.2.
- Use of a solar selective absorbing coating according to any of the above claims as coating of laminar materials or tubes selected from the group formed by steel, stainless steel, copper, aluminium, glass or polymeric materials for use in hot water, heating or home cooling systems.
- Use of a solar selective absorbing coating according to any of the above claims as coating of laminar materials or tubes selected from the group formed by steel, stainless steel, copper, aluminium or ceramic materials for use in the absorbing element of tower-type solar thermoelectric plants.
- Use of a solar selective absorbing coating according to any of the above claims as coating of laminar materials or tubes selected from the group formed by steel, stainless steel, copper, aluminium or ceramic materials for use in the absorbing element in "Stirling disk" systems.
- Use of a solar selective absorbing coating according to any of the above claims as coating of laminar materials or tubes selected from the group formed by steel, stainless steel, copper, aluminium or ceramic materials for use in the absorbing tube of solar thermoelectric plants of cylindrical-parabolic collectors.
- Manufacturing method of solar selective absorbing coating according to claims 1-22 unique because it consists in the stages of:- Addition of a first metallic layer (2) to a substrate (1) of metallic or dielectric material- On this first metallic layer (2) is deposited the first of the layers that forms the absorbing multilayer structure (3), which can be either dielectric (5) or metallic (6) material.- After this first layer of the absorbing multilayer structure (3) the rest of the metallic (6) and dielectric (5) layers are alternately deposited.- After the last of the layers of the absorbing multilayer structure (3), the different layers that form the anti-reflecting structure (4) are added.
- Manufacturing method of a solar selective absorbing coating according to claim 27 unique because of the use of a procedure of chemical vapour deposition (CVD) or physical vapour deposition (PVD) for the successive addition of different layers.
- Manufacturing method of a solar selective absorbing coating according to claim 28 unique because of the use of a procedure of "magnetron sputtering".
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES200802953A ES2316321B2 (en) | 2008-10-20 | 2008-10-20 | SOLAR SELECTIVE ABSORBENT COATING AND MANUFACTURING METHOD. |
PCT/ES2009/000489 WO2010046509A1 (en) | 2008-10-20 | 2009-10-08 | Selective solar absorbent coating and manufacturing method |
Publications (3)
Publication Number | Publication Date |
---|---|
EP2341038A1 true EP2341038A1 (en) | 2011-07-06 |
EP2341038A4 EP2341038A4 (en) | 2014-07-09 |
EP2341038B1 EP2341038B1 (en) | 2016-09-21 |
Family
ID=40434740
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09821624.5A Not-in-force EP2341038B1 (en) | 2008-10-20 | 2009-10-08 | Selective solar absorbent coating and manufacturing method |
Country Status (16)
Country | Link |
---|---|
US (2) | US9423157B2 (en) |
EP (1) | EP2341038B1 (en) |
JP (1) | JP2012506021A (en) |
CN (1) | CN102203024A (en) |
AU (1) | AU2009306317B2 (en) |
BR (1) | BRPI0920337A2 (en) |
CL (1) | CL2011000770A1 (en) |
EG (1) | EG26329A (en) |
ES (2) | ES2316321B2 (en) |
IL (1) | IL212256A (en) |
MA (1) | MA32706B1 (en) |
MX (1) | MX2011003864A (en) |
PE (1) | PE20120085A1 (en) |
TN (1) | TN2011000177A1 (en) |
WO (1) | WO2010046509A1 (en) |
ZA (1) | ZA201102742B (en) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102328475A (en) * | 2011-08-23 | 2012-01-25 | 北京天瑞星真空技术开发有限公司 | High-temperature solar selective absorption coating with SiO2 and TiO2 bi-ceramic structure and preparation method thereof |
CN102328476A (en) * | 2011-08-23 | 2012-01-25 | 北京天瑞星真空技术开发有限公司 | High-temperature solar energy selective absorption coating comprising TiO2 and Al2O3 double ceramic structures and preparation method thereof |
DE102011083166A1 (en) * | 2011-09-22 | 2013-03-28 | Von Ardenne Anlagentechnik Gmbh | Composite material for solar heat collector, has absorber comprising lower sublayer, which incorporates aluminum nitride compound, and upper sublayer, which incorporates silicon aluminum nitride compound |
CN103128518A (en) * | 2011-12-05 | 2013-06-05 | 常州天天太阳能有限公司 | Machining technology of solar air flat plate collector with plate core formed through blow molding |
WO2014045241A2 (en) | 2012-09-20 | 2014-03-27 | Ecole Polytechnique Federale De Lausanne (Epfl) | Method for hardening a coating of a solar collector element, and elements produced by means of said method |
ITMI20122162A1 (en) * | 2012-12-18 | 2014-06-19 | Consiglio Nazionale Ricerche | SOLAR ABSORBER INCLUDING TAB2 |
DE102013110118A1 (en) * | 2013-08-20 | 2015-02-26 | Von Ardenne Gmbh | Solar absorber and process for its production |
WO2017072711A1 (en) * | 2015-10-30 | 2017-05-04 | Rioglass Solar Systems Ltd. | Method for the deposition of functional layers suitable for heat receiver tubes |
US9746206B2 (en) | 2012-05-01 | 2017-08-29 | Dexerials Corporation | Heat-absorbing material and process for producing same |
EP3410030A4 (en) * | 2016-01-29 | 2019-07-03 | Kabushiki Kaisha Toyota Jidoshokki | Solar heat collection tube and production method therefor |
EP3410031A4 (en) * | 2016-01-29 | 2019-07-03 | Kabushiki Kaisha Toyota Jidoshokki | Solar heat collection tube |
EP3410032A4 (en) * | 2016-01-29 | 2019-07-10 | Kabushiki Kaisha Toyota Jidoshokki | Solar heat collection tube |
FR3078979A1 (en) * | 2018-03-15 | 2019-09-20 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | PROCESS FOR FORMING AN OXIDE LAYER (FE, CR) 2O3 OF A RHOMBOEDRIC STRUCTURE ON A STEEL SUBSTRATE |
EP3575706A4 (en) * | 2017-01-24 | 2020-07-08 | Nano Frontier Technology Co., Ltd. | Thermal collecting film for solar thermal power generation and manufacturing method for same |
Families Citing this family (63)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2316321B2 (en) | 2008-10-20 | 2010-12-14 | Abengoa Solar New Technologies, S.A. | SOLAR SELECTIVE ABSORBENT COATING AND MANUFACTURING METHOD. |
US8020314B2 (en) * | 2008-10-31 | 2011-09-20 | Corning Incorporated | Methods and apparatus for drying ceramic green bodies with microwaves |
US10654748B2 (en) | 2010-03-29 | 2020-05-19 | Vitro Flat Glass Llc | Solar control coatings providing increased absorption or tint |
US10654747B2 (en) | 2010-03-29 | 2020-05-19 | Vitro Flat Glass Llc | Solar control coatings with subcritical copper |
US9932267B2 (en) | 2010-03-29 | 2018-04-03 | Vitro, S.A.B. De C.V. | Solar control coatings with discontinuous metal layer |
JP5743487B2 (en) * | 2010-10-25 | 2015-07-01 | イビデン株式会社 | Heat collector tube, collector, and concentrating solar power generation system |
EP2666628A4 (en) * | 2011-01-13 | 2016-05-25 | Toray Industries | Far infrared reflecting laminate |
US8679633B2 (en) * | 2011-03-03 | 2014-03-25 | Guardian Industries Corp. | Barrier layers comprising NI-inclusive alloys and/or other metallic alloys, double barrier layers, coated articles including double barrier layers, and methods of making the same |
WO2012172148A1 (en) | 2011-06-16 | 2012-12-20 | Consejo Superior De Investigaciones Científicas (Csic) | Covering that selectively absorbs visible and infrared radiation, and method for the production thereof |
ES2401518B1 (en) * | 2011-06-16 | 2014-03-27 | Aurum Foods, S.L. | TUBULAR HEAT EXCHANGER. |
CN102261757B (en) * | 2011-07-06 | 2013-03-06 | 张浙军 | Solar collector core with silicon nitride medium selective absorption coating and preparation method |
CN102305487A (en) * | 2011-10-11 | 2012-01-04 | 李德杰 | Solar collector tube of multilayer metal dielectric film interference type |
FR2981646B1 (en) * | 2011-10-21 | 2013-10-25 | Saint Gobain | SOLAR CONTROL GLAZING COMPRISING A LAYER OF AN ALLOY NICU |
CN102384594A (en) * | 2011-10-31 | 2012-03-21 | 许培和 | Flat type solar water heater |
DE202011051927U1 (en) * | 2011-11-10 | 2013-02-11 | Alanod Aluminium-Veredlung Gmbh & Co. Kg | Laser weldable composite material |
CN102434990A (en) * | 2011-12-27 | 2012-05-02 | 李德杰 | Solar heat collecting pipe with scattering surface |
KR101424573B1 (en) * | 2012-03-16 | 2014-08-04 | 주식회사 강남 | absorbing plate for solar collector |
CN102689467A (en) * | 2012-05-23 | 2012-09-26 | 北京天瑞星光热技术有限公司 | A high temperature solar power selective absorption coating with a Si3N4 and AlN double ceramic structure and a preparation method thereof |
JP2015166637A (en) * | 2012-07-03 | 2015-09-24 | 旭硝子株式会社 | Light selective absorption film, heat collection tube and solar heat power generation device |
FR2995888B1 (en) * | 2012-09-21 | 2016-12-02 | Saint Gobain | SUBSTRATE HAVING A STACK WITH THERMAL PROPERTIES AND ABSORBENT LAYER. |
ITMI20121572A1 (en) * | 2012-09-21 | 2014-03-22 | Eni Spa | PROCEDURE FOR THE PRODUCTION OF AN OPTICALLY SELECTIVE CLADDING OF A SUBSTRATE FOR HIGH TEMPERATURE AND RELATIVE SOLAR RECEIVER DEVICES |
JP6059952B2 (en) | 2012-10-26 | 2017-01-11 | 株式会社豊田自動織機 | Heat conversion member and heat conversion laminate |
JP5896889B2 (en) * | 2012-12-07 | 2016-03-30 | 株式会社豊田自動織機 | Optical selective membrane |
CN103868252A (en) * | 2012-12-17 | 2014-06-18 | 广东工业大学 | Double-faced vortex phase-change energy storage solar energy constant temperature heating equipment |
CN103866231A (en) * | 2012-12-17 | 2014-06-18 | 广东工业大学 | Method for preparing solar selective absorbing coating |
UA117474C2 (en) * | 2013-02-14 | 2018-08-10 | Агк Гласс Юроп | Solar control glazing |
CN103255377B (en) * | 2013-05-20 | 2015-11-11 | 武汉大学 | A kind of nano combined Cr-Al-O solar spectrum Selective absorber coating and preparation method thereof |
DE102013112532A1 (en) * | 2013-11-14 | 2015-05-21 | Von Ardenne Gmbh | Radiation absorber for absorbing electromagnetic radiation, solar absorber arrangement, and method for producing a radiation absorber |
CN104534703B (en) * | 2013-11-28 | 2016-08-24 | 康雪慧 | A kind of solar selectively absorbing coating and preparation method thereof |
CN103770403B (en) * | 2013-12-31 | 2016-12-07 | 东莞南玻工程玻璃有限公司 | A kind of can the heat-reflection coated glass of tempering |
MX2014001213A (en) * | 2014-01-29 | 2015-07-29 | En Suministros E Instalaciones S A De C V | Selective absorbent coating of radiation and process for obtaining the same at room temperature. |
CN104947054A (en) * | 2014-03-28 | 2015-09-30 | 北京桑达太阳能技术有限公司 | Preparation method of solar spectrum selective absorbing coating |
CN104949362A (en) * | 2014-03-28 | 2015-09-30 | 北京桑达太阳能技术有限公司 | Solar spectrum selective absorbing coating |
WO2015190840A1 (en) * | 2014-06-12 | 2015-12-17 | 주식회사 케이씨씨 | Multilayer coated substrate for reflecting rear surface of solar battery module and manufacturing method therefor |
DE102015215006A1 (en) | 2014-08-06 | 2016-02-18 | Council Of Scientific & Industrial Research | Improved multilayer solar selective coating for high temperature solar thermal |
DE102014113958A1 (en) * | 2014-09-26 | 2016-03-31 | Endress + Hauser Gmbh + Co. Kg | Method for establishing a connection between two ceramic parts, in particular parts of a pressure sensor |
WO2016069174A1 (en) * | 2014-10-29 | 2016-05-06 | University Of Houston System | Enhanced thermal stability on multi-metal filled cermet based spectrally selective solar absorbers |
JP6565608B2 (en) * | 2014-12-02 | 2019-08-28 | 株式会社デンソー | Coating structure, heat exchanger, and method of manufacturing heat exchanger |
CN104596137A (en) * | 2014-12-02 | 2015-05-06 | 浙江大学 | Graphite nano-crystalline dielectric composite film structure and application |
CN107405876B (en) * | 2015-03-17 | 2020-12-25 | 麦格纳国际公司 | Non-metallic coating for steel substrates and method of forming the same |
CN104930735A (en) * | 2015-03-24 | 2015-09-23 | 江苏奥蓝工程玻璃有限公司 | Solar absorbing film and preparation method thereof |
US10539726B2 (en) * | 2015-09-01 | 2020-01-21 | Vitro Flat Glass Llc | Solar control coating with enhanced solar control performance |
CN106813408A (en) * | 2016-09-07 | 2017-06-09 | 山东圣泉新材料股份有限公司 | A kind of solar selectively absorbing coating, preparation method and purposes |
CN106958005A (en) * | 2017-03-31 | 2017-07-18 | 中国科学院宁波材料技术与工程研究所 | A kind of refractory metal ceramic solar spectral selective absorbing coating and preparation method |
JP2018185446A (en) * | 2017-04-27 | 2018-11-22 | セイコーエプソン株式会社 | Anti-reflection film, optical device, and method for manufacturing anti-reflection film |
US10556823B2 (en) * | 2017-06-20 | 2020-02-11 | Apple Inc. | Interior coatings for glass structures in electronic devices |
CN107461948A (en) * | 2017-08-03 | 2017-12-12 | 山东圣泉新材料股份有限公司 | A kind of solar selectively absorbing coating, its preparation method and photothermal conversion device |
JP6907876B2 (en) * | 2017-10-19 | 2021-07-21 | 株式会社村田製作所 | Film formation method |
FR3073865B1 (en) * | 2017-11-17 | 2022-05-27 | Centre Nat Rech Scient | COATING FOR SOLAR RECEIVER AND DEVICE COMPRISING SUCH COATING |
KR102051730B1 (en) * | 2018-01-12 | 2019-12-04 | 한양대학교 산학협력단 | Phase shifter mask that comprising spacer pattern and phase shift pattern, and fabricating method of the same |
US11951710B2 (en) | 2018-01-19 | 2024-04-09 | Osaka Gas Co., Ltd. | Radiative cooling device |
KR102133080B1 (en) * | 2018-05-09 | 2020-07-13 | 전자부품연구원 | Multi-layered thin film structure, thermal emitter and manufacturing method thereof |
CN111971592B (en) | 2018-07-23 | 2023-03-28 | 大阪瓦斯株式会社 | Radiation cooling device |
CN109285827B (en) * | 2018-08-31 | 2019-05-31 | 深亮智能技术(中山)有限公司 | A kind of crystal circle structure and its test method |
CN109052379A (en) * | 2018-09-04 | 2018-12-21 | 山西大学 | A kind of preparation method of blacker-than-black light absorbent |
CN110895058A (en) * | 2018-09-13 | 2020-03-20 | 康楚钒 | Novel high-temperature solar selective absorption coating |
CN108957604A (en) * | 2018-09-27 | 2018-12-07 | 中国计量大学 | A kind of multilayered structure absorbed with selection |
CN110422345B (en) * | 2019-07-26 | 2022-07-19 | 中国电子科技集团公司第三十三研究所 | OSR thermal control coating based on photonic crystal |
WO2021085895A1 (en) * | 2019-10-31 | 2021-05-06 | 고려대학교 산학협력단 | Radiant cooling element and method for manufacturing same |
DE102019131429A1 (en) * | 2019-11-21 | 2021-05-27 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Layer system reducing interference radiation |
CN114623611A (en) * | 2020-12-14 | 2022-06-14 | 宋太伟 | Efficient reflection-reducing photothermal film structure process for single-layer or multi-layer nanowire net thin layer |
CN114623610A (en) * | 2020-12-14 | 2022-06-14 | 宋太伟 | Light-absorbing thermal film structure process for laminating metal and nonmetal nano film |
IT202200012065A1 (en) * | 2022-06-07 | 2023-12-07 | Enea Agenzia Naz Per Le Nuove Tecnologie Lenergia E Lo Sviluppo Economico Sostenibile | Spectrally selective absorber coating for solar receivers operating in air |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0027718A1 (en) * | 1979-10-18 | 1981-04-29 | Optical Coating Laboratory, Inc. | Articles having optical properties, selective solar absorbers and solar heating structures |
US4282290A (en) * | 1980-01-23 | 1981-08-04 | The United States Of America As Represented By The Secretary Of The Air Force | High absorption coating |
EP0107412A1 (en) * | 1982-10-08 | 1984-05-02 | The University Of Sydney | Solar selective surface coating |
US5523132A (en) * | 1991-07-19 | 1996-06-04 | The University Of Sydney | Thin film solar selective surface coating |
WO1997000335A1 (en) * | 1995-06-19 | 1997-01-03 | The University Of Sydney | Solar selective surface coating |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3272986A (en) * | 1963-09-27 | 1966-09-13 | Honeywell Inc | Solar heat absorbers comprising alternate layers of metal and dielectric material |
CH595458A5 (en) * | 1975-03-07 | 1978-02-15 | Balzers Patent Beteilig Ag | |
US4437455A (en) * | 1982-05-03 | 1984-03-20 | Engelhard Corporation | Stabilization of solar films against hi temperature deactivation |
US4582764A (en) * | 1982-09-24 | 1986-04-15 | Energy Conversion Devices, Inc. | Selective absorber amorphous alloys and devices |
DE3538390A1 (en) * | 1985-10-29 | 1987-04-30 | Deutsche Forsch Luft Raumfahrt | COATING FOR A SUBSTRATE AND METHOD FOR THE PRODUCTION THEREOF |
JPH0222863A (en) | 1988-07-11 | 1990-01-25 | Mitsubishi Electric Corp | Semiconductor integrated circuit package device |
CA2120875C (en) * | 1993-04-28 | 1999-07-06 | The Boc Group, Inc. | Durable low-emissivity solar control thin film coating |
NO303045B1 (en) | 1995-06-16 | 1998-05-25 | Terje Steinar Olsen | Chair with foot / leg support |
DE10016008A1 (en) * | 2000-03-31 | 2001-10-11 | Zeiss Carl | Village system and its manufacture |
DE20021644U1 (en) * | 2000-12-20 | 2002-05-02 | ALANOD Aluminium-Veredlung GmbH & Co.KG, 58256 Ennepetal | Solar collector element |
US7405872B2 (en) * | 2003-05-28 | 2008-07-29 | Astic Signals Defenses Llc | System and method for filtering electromagnetic transmissions |
US20040126594A1 (en) | 2002-06-06 | 2004-07-01 | Carlo Rubbia | Surface coating for a collector tube of a linear parabolic solar concentrator |
US6707610B1 (en) * | 2002-09-20 | 2004-03-16 | Huper Optik International Pte Ltd | Reducing the susceptibility of titanium nitride optical layers to crack |
DE102004010689B3 (en) | 2004-02-27 | 2005-06-30 | Schott Ag | Absorber with radiation-selective absorber coating for use of thermic solar energy has oxide diffusion blocking layer provided by oxidized components of metal substrate |
ITRM20040279A1 (en) | 2004-06-07 | 2004-09-07 | Enea Ente Nuove Tec | SPECTRALLY SELECTIVE SURFACE COATING OF THE RECEIVER TUBE OF A SOLAR CONCENTRATOR, AND METHOD FOR ITS MANUFACTURE. |
JP4423119B2 (en) * | 2004-06-16 | 2010-03-03 | キヤノン株式会社 | Antireflection film and optical element using the same |
DE102004038233A1 (en) | 2004-08-05 | 2006-03-16 | Schott Ag | solar absorber |
US7335421B2 (en) * | 2005-07-20 | 2008-02-26 | Ppg Industries Ohio, Inc. | Heatable windshield |
US8893711B2 (en) * | 2007-10-18 | 2014-11-25 | Alliance For Sustainable Energy, Llc | High temperature solar selective coatings |
ES2316321B2 (en) | 2008-10-20 | 2010-12-14 | Abengoa Solar New Technologies, S.A. | SOLAR SELECTIVE ABSORBENT COATING AND MANUFACTURING METHOD. |
DE102015215006A1 (en) | 2014-08-06 | 2016-02-18 | Council Of Scientific & Industrial Research | Improved multilayer solar selective coating for high temperature solar thermal |
-
2008
- 2008-10-20 ES ES200802953A patent/ES2316321B2/en not_active Expired - Fee Related
-
2009
- 2009-10-08 WO PCT/ES2009/000489 patent/WO2010046509A1/en active Application Filing
- 2009-10-08 BR BRPI0920337A patent/BRPI0920337A2/en not_active Application Discontinuation
- 2009-10-08 ES ES09821624.5T patent/ES2608031T3/en active Active
- 2009-10-08 EP EP09821624.5A patent/EP2341038B1/en not_active Not-in-force
- 2009-10-08 US US13/123,695 patent/US9423157B2/en not_active Expired - Fee Related
- 2009-10-08 MX MX2011003864A patent/MX2011003864A/en unknown
- 2009-10-08 PE PE2011000855A patent/PE20120085A1/en not_active Application Discontinuation
- 2009-10-08 CN CN200980140635.9A patent/CN102203024A/en active Pending
- 2009-10-08 AU AU2009306317A patent/AU2009306317B2/en not_active Ceased
- 2009-10-08 JP JP2011531521A patent/JP2012506021A/en active Pending
-
2011
- 2011-04-07 CL CL2011000770A patent/CL2011000770A1/en unknown
- 2011-04-11 IL IL212256A patent/IL212256A/en not_active IP Right Cessation
- 2011-04-12 MA MA33764A patent/MA32706B1/en unknown
- 2011-04-12 ZA ZA2011/02742A patent/ZA201102742B/en unknown
- 2011-04-12 EG EG2011040564A patent/EG26329A/en active
- 2011-04-15 TN TN2011000177A patent/TN2011000177A1/en unknown
-
2015
- 2015-03-30 US US14/673,548 patent/US10126020B2/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0027718A1 (en) * | 1979-10-18 | 1981-04-29 | Optical Coating Laboratory, Inc. | Articles having optical properties, selective solar absorbers and solar heating structures |
US4282290A (en) * | 1980-01-23 | 1981-08-04 | The United States Of America As Represented By The Secretary Of The Air Force | High absorption coating |
EP0107412A1 (en) * | 1982-10-08 | 1984-05-02 | The University Of Sydney | Solar selective surface coating |
US5523132A (en) * | 1991-07-19 | 1996-06-04 | The University Of Sydney | Thin film solar selective surface coating |
WO1997000335A1 (en) * | 1995-06-19 | 1997-01-03 | The University Of Sydney | Solar selective surface coating |
Non-Patent Citations (1)
Title |
---|
See also references of WO2010046509A1 * |
Cited By (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102328476A (en) * | 2011-08-23 | 2012-01-25 | 北京天瑞星真空技术开发有限公司 | High-temperature solar energy selective absorption coating comprising TiO2 and Al2O3 double ceramic structures and preparation method thereof |
CN102328475B (en) * | 2011-08-23 | 2013-12-18 | 北京天瑞星光热技术有限公司 | High-temperature solar selective absorption coating with SiO2 and TiO2 bi-ceramic structure and preparation method thereof |
CN102328476B (en) * | 2011-08-23 | 2014-03-12 | 北京天瑞星光热技术有限公司 | High-temperature solar energy selective absorption coating comprising TiO2 and Al2O3 double ceramic structures and preparation method thereof |
CN102328475A (en) * | 2011-08-23 | 2012-01-25 | 北京天瑞星真空技术开发有限公司 | High-temperature solar selective absorption coating with SiO2 and TiO2 bi-ceramic structure and preparation method thereof |
DE102011083166A1 (en) * | 2011-09-22 | 2013-03-28 | Von Ardenne Anlagentechnik Gmbh | Composite material for solar heat collector, has absorber comprising lower sublayer, which incorporates aluminum nitride compound, and upper sublayer, which incorporates silicon aluminum nitride compound |
DE102011083166B4 (en) * | 2011-09-22 | 2017-08-17 | Von Ardenne Gmbh | Composite material with spectrally selective multilayer system and method for its production |
CN103128518B (en) * | 2011-12-05 | 2015-11-25 | 常州海卡太阳能热泵有限公司 | The processing technology of the solar air flat plate collector that plate core inflation is shaping |
CN103128518A (en) * | 2011-12-05 | 2013-06-05 | 常州天天太阳能有限公司 | Machining technology of solar air flat plate collector with plate core formed through blow molding |
US9746206B2 (en) | 2012-05-01 | 2017-08-29 | Dexerials Corporation | Heat-absorbing material and process for producing same |
WO2014045241A2 (en) | 2012-09-20 | 2014-03-27 | Ecole Polytechnique Federale De Lausanne (Epfl) | Method for hardening a coating of a solar collector element, and elements produced by means of said method |
ITMI20122162A1 (en) * | 2012-12-18 | 2014-06-19 | Consiglio Nazionale Ricerche | SOLAR ABSORBER INCLUDING TAB2 |
WO2014097165A3 (en) * | 2012-12-18 | 2014-10-30 | Consiglio Nazionale Delle Ricerche | SOLAR ABSORBER COMPRISING TaB2 |
DE102013110118B4 (en) * | 2013-08-20 | 2016-02-18 | Von Ardenne Gmbh | Solar absorber and process for its production |
DE102013110118A1 (en) * | 2013-08-20 | 2015-02-26 | Von Ardenne Gmbh | Solar absorber and process for its production |
WO2017072711A1 (en) * | 2015-10-30 | 2017-05-04 | Rioglass Solar Systems Ltd. | Method for the deposition of functional layers suitable for heat receiver tubes |
CN108351124A (en) * | 2015-10-30 | 2018-07-31 | 里奥玻璃太阳能***有限公司 | A method of functional layer of the deposition suitable for heated absorption tube |
CN108351124B (en) * | 2015-10-30 | 2020-04-28 | 里奥玻璃太阳能***有限公司 | Method for depositing functional layer suitable for heat absorption tube |
EP3410030A4 (en) * | 2016-01-29 | 2019-07-03 | Kabushiki Kaisha Toyota Jidoshokki | Solar heat collection tube and production method therefor |
EP3410031A4 (en) * | 2016-01-29 | 2019-07-03 | Kabushiki Kaisha Toyota Jidoshokki | Solar heat collection tube |
EP3410032A4 (en) * | 2016-01-29 | 2019-07-10 | Kabushiki Kaisha Toyota Jidoshokki | Solar heat collection tube |
US11231208B2 (en) | 2016-01-29 | 2022-01-25 | Kabushiki Kaisha Toyota Jidoshokki | Solar heat collector tube |
US11149987B2 (en) | 2016-01-29 | 2021-10-19 | Kabushiki Kaisha Toyota Jidoshokki | Solar heat collector tube and production method thereof |
US11009264B2 (en) | 2016-01-29 | 2021-05-18 | Kabushiki Kaisha Toyota Jidoshokki | Solar heat collector tube |
US11002466B2 (en) | 2017-01-24 | 2021-05-11 | Nano Frontier Technology Co., Ltd. | Absorber coating for solar heat power generation and manufacturing method thereof |
EP3575706A4 (en) * | 2017-01-24 | 2020-07-08 | Nano Frontier Technology Co., Ltd. | Thermal collecting film for solar thermal power generation and manufacturing method for same |
WO2019186024A3 (en) * | 2018-03-15 | 2019-11-21 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method for forming a layer of single-phase oxide (fe, cr)2o3 with a rhombohedral structure on a steel or super alloy substrate |
FR3078979A1 (en) * | 2018-03-15 | 2019-09-20 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | PROCESS FOR FORMING AN OXIDE LAYER (FE, CR) 2O3 OF A RHOMBOEDRIC STRUCTURE ON A STEEL SUBSTRATE |
US11965253B2 (en) | 2018-03-15 | 2024-04-23 | Mannesmann Precision Tubes France | Method for forming a layer of single-phase oxide (Fe, Cr)2O3 with a rhombohedral structure on a steel or super alloy substrate |
Also Published As
Publication number | Publication date |
---|---|
US9423157B2 (en) | 2016-08-23 |
EG26329A (en) | 2013-08-13 |
EP2341038A4 (en) | 2014-07-09 |
US20110249326A1 (en) | 2011-10-13 |
ES2316321B2 (en) | 2010-12-14 |
EP2341038B1 (en) | 2016-09-21 |
WO2010046509A1 (en) | 2010-04-29 |
TN2011000177A1 (en) | 2012-12-17 |
ZA201102742B (en) | 2011-12-28 |
CL2011000770A1 (en) | 2011-09-30 |
AU2009306317B2 (en) | 2015-07-30 |
PE20120085A1 (en) | 2012-02-08 |
BRPI0920337A2 (en) | 2016-03-01 |
CN102203024A (en) | 2011-09-28 |
ES2608031T3 (en) | 2017-04-05 |
AU2009306317A1 (en) | 2010-04-29 |
IL212256A (en) | 2017-09-28 |
US10126020B2 (en) | 2018-11-13 |
IL212256A0 (en) | 2011-06-30 |
MX2011003864A (en) | 2011-08-12 |
JP2012506021A (en) | 2012-03-08 |
ES2316321A1 (en) | 2009-04-01 |
US20150267303A1 (en) | 2015-09-24 |
MA32706B1 (en) | 2011-10-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10126020B2 (en) | Selective solar absorbing coating and manufacturing method | |
EP1759031B1 (en) | Spectrally selective surface coating of the receiver tube of a solar concentrator, and method for the manufacture thereof | |
US8318329B2 (en) | Radiation-selective absorber coating, absorber tube and process for production thereof | |
Valleti et al. | Functional multi-layer nitride coatings for high temperature solar selective applications | |
CN101408354B (en) | Solar selective absorption coating and preparing method thereof | |
EP2722612A1 (en) | Covering that selectively absorbs visible and infrared radiation, and method for the production thereof | |
CN101666557B (en) | Non-vacuum solar spectrum selective absorption film and preparation method thereof | |
EP3240978A1 (en) | Self-cleaning high temperature resistant solar selective structure | |
US20140144426A1 (en) | Covering that selectively absorbs visible and infrared radiation, and method for the production thereof | |
US20120270023A1 (en) | Composite material | |
WO2016155407A1 (en) | A spectrally selective solar absorbing coating and a method for making it | |
EP2245208A2 (en) | Method for producing a cermet-based spectrally selective coating and material thus obtained | |
CN106468483A (en) | A kind of new stacked structure photothermal deformation coating | |
US20230349595A1 (en) | Spectrally selective solar absorber coating | |
EP3433546B1 (en) | Solar selective coating | |
CN109881155B (en) | Intelligent selective sunlight transmission and reflection coating and preparation method thereof | |
WO2002103257A1 (en) | Surface coating of the collector tube of a linear parabolic solar concentrator | |
WO2023237475A1 (en) | Spectrally selective absorbing coating for solar receivers acting in air | |
Nasov et al. | RESEARCH, DEVELOPMENT AND INOVATION FOR UTILIYING RENEWABLE SOLAR ENERGY: POLYMER SOLAR THERMAL COLLECTORS | |
RU2407958C2 (en) | Multilayer selective absorbing coating for solar collector and method of making said coating | |
Zhiqiang et al. | Sputtered Aluminium Composite Selective Absorbing Surfaces |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20110414 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA RS |
|
DAX | Request for extension of the european patent (deleted) | ||
A4 | Supplementary search report drawn up and despatched |
Effective date: 20140612 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C03C 17/36 20060101AFI20140605BHEP Ipc: F24J 2/46 20060101ALI20140605BHEP Ipc: C23C 28/00 20060101ALI20140605BHEP Ipc: F24J 2/48 20060101ALI20140605BHEP |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20160419 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 830897 Country of ref document: AT Kind code of ref document: T Effective date: 20161015 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602009041319 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D Ref country code: NL Ref legal event code: MP Effective date: 20160921 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160921 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161221 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160921 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 830897 Country of ref document: AT Kind code of ref document: T Effective date: 20160921 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20161031 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160921 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160921 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161222 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160921 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2608031 Country of ref document: ES Kind code of ref document: T3 Effective date: 20170405 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160921 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160921 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161221 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170121 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160921 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170123 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160921 Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160921 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160921 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160921 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160921 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602009041319 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160921 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20170630 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20161121 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160921 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20161031 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20161031 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20161221 |
|
26N | No opposition filed |
Effective date: 20170622 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20161008 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20161221 Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160921 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20161008 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160921 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20091008 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160921 Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160921 Ref country code: MT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20161031 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160921 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160921 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20190401 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20190725 Year of fee payment: 10 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602009041319 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200501 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20210302 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20191009 |